Azine compounds and materials colored therewith



Patented Apr. 15, 1941 AZINE COMPOUNDS AND MATERIALS COLORED THE-REWITHJoseph B. Dickey and James G. MoN-ally, Rochester, N. Y., assignors toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. .Application July 24,

Serial No. 347,219

6 Claims.

The present invention relates to azine compounds and to materialscolored therewith. More particularly, it relates to ,azine compoundshaving the general formula:

wherein Z1 represents the non-metallic atoms necessary to complete abenzene nucleus, Z2 represents the non-metallic atoms necessary tocomplete an aryl nucleus selected from the group consisting of a benzenenucleus, a naphthalene nucleus, and a phenanthrene nucleus, and Xrepresents a member selected from the group consisting of an oxygenatom, a sulphur atom, a nitrogen atom, and an imide group, and whereinZ1 contains at least one alkylamino group, and Z1 and Z2 togethercontain at least one acid ester of phosphorus group joined to the omegacarbon atom of anon-cyclic organic sidechain. These compounds areusually prepared in the form of their quaternary salts such as thechloride, sulfate, chlorate, sulfonate, and the like. While they areconsidered mostly as having the p quinonoid structure, it will beunderstood that they are subject to tautomeric change to the oquinonoidform.

More specifically, the acid ester of phosphorus group can be representedby the ganeral formula:

wherein ,n. represents zero or the numeral 1. R1 and R2 each representsan amino group, an alkylamino group such as methylamino, ethylamino,propylamino, butylamino, cetylamino, methoxyethylamino for example, andthe group OZ, wherein Z represents hydrogen, an alkyl group such asmethyl, ethyl, propyl, butyl, cetyl, an alkali forming metal such assodium, potassium, calcium, barium, a nitrogen containing basic groupsuch as an ammonium radical, and organic amine salts of the free acidsuch as the dimethylamine salt, the ethanolamine salt, thediethanolamine salt for example, and X representsan atom of oxygen or anatom of'sulphur. The sidechain can be represented by the radicals suchas.

and other similar kind of radicals. Further, the "nuclei Z, and Z2, inaddition to Z1 containing at least one al'kylamino group and Z1 and Z2together containing at least one acid ester of phosphorus group in asldeehain, can also contain other mcnovalent substituent groups such asmethyl, ethyl, propyl, methoxy, ethoxy, amino, methyl-'amino,-ethylamino, hydroxyl, and atoms such as chlorine and bromine. 1

We have found that the azine compounds above described form a valuableseries of coloring agents for textile materials such as organicderivatives of cellulose, wool, silk and mordanted cottons, as well asdyes for anti-halation backing compositionsfor photographic films. Thetinting power of our new dyes range in color from green to blue. Thematerials colored by these dyes exhibit good stability to light andatmospheric exposure. The water-soluble feature of our new dyes isparticularly advantageous in the case of anti-halation backings, sincethe dyes can be removed quiteeasily during the process of developmentand fixation of the photographic film.

It is an object of our invention, therefore, to prepare the compoundsdescribed. A further object is to color textile materials therewith.Another object is to prepare backing compositions containing our newdyes.

The azine compounds of the invention can be prepared by startinginitially with the dye nucleus already formed and containing one or moresubstituent groups having a hydroxyl roup, or, groups such as aminowhich can be converted to ah'ydroxyalkylamino group by reaction with analkyleneoxide such as ethylene oxide, or, nuclear hydroxylgroups whichcan be converted to a hydroxyalkoxygroup by reaction with'an alkylenechlorhydrin, and phosphating the hydroxyl groupsuitable phosphatingagents include compounds such as phosphorus oxychloride,

phosphorus sulfochloride, phosphorus trichloride, phosphoric acid,tetraphosphoric acid, thiophosphoric acid, phosphoric anhydride,phosphorus oxydichloride, methoxy phosphorus oxymonochloride, aminophosphorus oxydichloride, methylamino phosphorus oxydichloride andvarious other alkoxy and substituted amino phosphorus compounds. Thephosphating intermediates may be prepared as described in McNally andDickey U. S. Patent No. 2,183,998, December 19, 1939. Another method ofpreparing the dye compounds of the invention is to start withintermediates such as a paranitrosoaniline and con dense it with acompound such as a 2,6-diphenyl naphthylene diamine, adialkyl-m-amino-p-cresol, and the like, or, start with apara-alkylaminodiphenylamine and condense it with a compound such asphenanthrene for example. The phosphorus acid ester groups can bepresent originally in one or both of the starting materials or such acidester groups can be formed by simple esterification of nuclear hydroxylgroups or hydroxyl groups contained as substituents on the omega carbonatom of non-cyclic organic sidechains.

The following examples further illustrate the compounds of ourinvention, their methods of preparation and their applications. It willbe understood that these examples are not intended to limit ourinvention.

Example 1 1 mole of 3-hydroxy-7-amino-paraphenothiazine chloride istreated with approximately 2 molar equivalents of ethylenchlorhydrin,and the product obtained is dissolved in pyridine and condensed with 2molar equivalents of methoxy phosphorus oxydichloride dissolved inpyridine or dimethylaniline. The reaction is completed by warming, afterwhich the halogen remaining on the phosphorus is hydrolyzed with aqueoussodium carbonate, from which the ammonium salt may be prepared. The dyeobtained has the probable formula:

and colors cellulose acetate blue shades from an aqueous solution whichmay contain salt.

In place of methoxy phosphorus oxydichloride there can be substituted anequivalent amount of methoxy phosphorus dichloride, in which case thereis obtained the trivalent phosphorus dye- 39-methylphosphitoethoxy-7-p-methylphospitoethyllamino-phenothiazinechfloride. Various other phosphating agents may be used includingphosphorus trichloride.

Example 2 1 mole of 1-methylcarboxy-3,4-dihydroxy- 7 (di-p-hydrozqethyl) amino-paraphenoxazlne chloride is dissolved in pyridine andtreated in the cold with approximately 1.1 moles of phosphorusoxychloride. The reaction is completed by warming, after which thehalogen remaining on the phosphorus atom is hydrolyzed with aqueoussodium carbonate. The dye obtained has the formula:

COOCH:

and colors cellulose acetate and mordanted cotton blue shades from anaqueous solution of the dye. Any desired basic salt such as anmionium,piperidine, methylamine, calcium, and the like, can be prepared. Inplace of the phosphorus oxychloride exployed in the above example, theremay be substituted phosphorus sulfochloride, in

which case there is obtained the corresponding thiophosphoric acid esterderivative.

Example 3 In a manner similar to that described in Example 2, there iscondensed together approximately equal molar proportions ofl-methylcarboxy- 3,4-dihydroxy- 7 cetyl phydroxyethylaminoparaphenoxazine chloride and phosphorus trichloride,the compound obtained being a phosphorus acid ester having the formula:

COOCH:

and coloring cellulose acetate and mordanted cotton blue shades from anaqueous solution or the dye.

Example 4 1 mole of gallocyanine is reacted in the cold, in the presenceof an oxidizing agent such as air, with approximately 1 mole ofamino-ethyl phosphate. After the initial reaction is complete, theproduct is deoarboxylated by heating at C. The dye obtained has theprobable formula:

(C ozN 0 and colors cellulose acetate blue shades from an aqueoussolution which may contain salt.

Example 5 I Cl CHaO and colors cellulose acetate blue shades from anaqueous suspension of the dye.

In place' of 4-nitroso-l-ethyl-fl-dimethyl phosphatoethylamino-benzene,there can be substituted. an equivalent amount of 4-nitroso-1-(di- 5phenyl phosphitoethyl) amino-benzene, the product obtained having theprobable formula:

and coloring cellulose acetate, Wool and silk blue and the dye allowedto crystallize from. solution. The dye obtained has the formula:

CzHs I CH \N shades. l5 Example 6 I I O 1 mole of2-(N-di-c-hydroxyethyl) phenylene- N I I vp-diamino-B-amino-l-(di-fi-hydroxyethyl) amino-phenazine chloride istreated in pyridine with 2 molar equivalents of phosphorus oxychloride.110 The resulting chloro compound is hydrolyzed with O C H N 2 4 01sodium carbonate, neutralized with mmeral acid 11 cans and'the'diethanolamine salt prepared. The dye NHZ 0 obtained has theprobable formula: Cellulose acetate is colored green shades from N/C2H,OH 8 9 40 l 2 NH-C N OH.HN(CzHlOH)z Ho-o2Hl 7 oaHr-O-P(HOC2H4)QNH.HO N= 6 5 4 NH:

. v N ounmmmom,

P-O-O2HA 01 1 and colors cellulose acetate violet shades from an aqueoussolution which may contain salt.

Example 7 v 1 mole of 2-amino--ethyl-fl-disodiumphosphatoethylamino-diphenylamine is heated with approximately 1 mole ofphenanthrenequinone in 6000 c. c. of acetic acid on a water bath untilaportion of the reaction mixture boiled with an excess of water andacidified with hydrochloric acid shows no increase in intensity ofcolor. The melt is thenboiled with 6000 c. c. of water, acidified withhydrochloric acid and salted out. The dye obtained has the probableformula:

Similar dye compounds can be prepared by employing other phosphorusester derivatives. For example, the condensation of molar equivalents of2-amino--butyl-p-dimethyl phosphitoethyl-amino-diphenylamine andphenanthrenequinone gives the dye compound 9-phenyl-12-butyl-fl-dimethyl phosphitoethylamino-a, 'y-dibenzophenazine chloridewhich colors silk, wool and mordanted cotton orange shades.

Example 8 1 mole of 4-nitroso-1-ethyl-[3-(diethylamino) phosphorusoxyethylaminobenzene hydrochloride is heated in alcohol withapproximately 1 mole of 2,6-diphenyl-naphthalene diamine. When thereaction is complete, the alcohol is concentrated an aqueous solutionwhich may contain saltq Wool is also colored green shades from an acidbath.

Cellulose acetate is colored blue shades from an aqueous solution of thedye which may contain salt.

onml 0 Cellulose acetate is colored green shades from an aqueoussolution which may contain salt.

/OCH3 0112-0-1 v Cellulose acetate, wool and silk are colored blueshades from an aqueous solution of the dye.

The new dye compounds of our invention can r ordinarily be applied tothe textile material to be colored directly from an aqueous solution 01'the dye which may contain salt. As textile materials there can beemployed organic derivatives of cellulose such as cellulose acetate, andnatural fibers such as wool, silk and cotton. In some cases where theparticular dye compound is only moderately water-soluble, it will befound that the addition of a dispersing agent such as a soap, asulfonated oil or a fatty acid glyceryl sulfate is advantageous. Morespecifically, the dyeing operation can be conducted as follows:

2.5 parts by weight of the dye, prepared according to any of theexamples described, are dissolved in 230 parts of water and the'mixtureheated to about 80-85" C. at which point it is maintained throughout theentire dyeing operation. Then 100 parts of a textile material such ascellulose acetate, for example, is immersed in the dye solution andworked until the color acquired is considered satisfactory. Salt may beadded during the dyeing operation to promote exhaustion of the dye bath.The material is then removed from the bath, washed with soap, rinsed anddried. It will be colored green to blue shades depending on theparticular dye compound employed.

While our invention has been illustrated more particularly in connectionwith cellulose acetate, wool and silk, it will be understood that ournew phosphated azine compounds are likewise applicable as dyes for othercellulosic derivatives including the hydrolyzed as well as theunhydrolyzed organic acid esters of cellulose and mixed organic acidesters of cellulose such as cellulose formate, cellulose acetate,cellulose propionate, cellulose butyrate, cellulose phthalate, celluloseacetate-propionate, cellulose acetate-butyrate and cellulose ethers suchas methyl cellulose, ethyl cellulose, benzyl cellulose, and the like.

We claim:

1. The azine compounds selected from the group consisting of aphenothiazine nucleus, a

phenoxazine nucleus, a phenazine nucleus, and an a, -dibenzophenazinenucleus, each of said nuclei containing as nuclear carbon atomsubstituents at least one alkylamino group and at least one acid esterof phosphorus group joined to the omega carbon atom of a non-cyclicorganic sidechain.

2. The azine compounds having the general formula:

wherein Z1 represents the non-metallic atoms necessary to complete abenzene nucleus, Z2 represents the non-metallic atoms necessary tocomplete an aryl nucleus selected from the group consisting of a benzenenucleus, a naphthalene nucleus, and a phenanthrene nucleus, and Xrepresents a member selected from the group consisting of an atom ofoxygen, an atom of sulphur, an atom of nitrogen, and an imide group, andwherein Z1 contains .at least one alkylamino group, and Z1 and Z2together contain at least one acid ester of phosphorus group joined tothe omega carbon atom of a non-cyclic organic sidechain.

3. The azine compounds selected from the group consisting of aphenothiazine nucleus, 9. phenoxazine nucleus, 2. phenazine nucleus, andan a, y-dibenzophenazine nucleus, each of said nuclei containing asnuclear carbon atom substituents at least one alkylamino group and atleast one acid ester of phosphorus group having the general formula:

wherein n is selected from the group consisting of zero and the numeral1, R1 and R2 each represents a member selected from the group consistingof an amino group, an alkylamino group, and the group -OZ, wherein Zrepresents a member selected from the group consisting of hydrogen, analkyl group, and an alkali forming metal, the said acid ester groupbeing joined to the omega carbon atom of a non-cyclic organic sidechain.

4. The azine compounds selected from the group consisting of aphenothiazine nucleus, a phenoxazine nucleus, a phenazine nucleus, andan a, 'y-dibenzophenazine nucleus, each of said nuclei containing asnuclear carbon atom substituents at least one alkylamino group and atleast one acid ester of phophorus group joined to the omega carbon atomof an alkylamino group.

5. An organic derivative of cellulose textile material colored with adye selected from the group of azine compounds consisting of aphenothiazine nucleus, a phenoxazine nucleus, a phenazine nucleus, andan a, -dibenzophenazine nucleus, each of said nuclei containing asnuclear substituents at least one alkylamino group and at least one acidester of phosphorus group joined to the omega carbon atom of anon-cyclic organic sidechain.

6. A cellulose acetate textile material colored with a dye selected fromthe group of azine compounds consisting of a phenothiazine nucleus, aphenoxazine nucleus, a phenazine nucleus, and an a, 'y-dibenzophenazinenucleus, each of said nuclei containing as nuclear substituents at leastone alkylamino group and at least one acid ester of phosphorus groupjoined to the omega carbon atom of a non-cyclic organic sidechaln.

JOSEPH B.'DIC'KEY. JAMES G. MCNALLY.

